JPH0195142A - Preparation of thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the title compsn. having excellent mechanical strength, impact resistance, etc., by adding polypropylene, halogenated butyl rubber, a metal oxide and/or a metal chloride to a specified blend and crosslinking it while it is dynamically heat-treated. CONSTITUTION:A blend (C) is obtd. by heat-treating dynamically polypropylene (A) which is a (co)polymer of propylene and, if necessary, alpha-olefin and whose MFR is 0.3-80g/10min, a crosslinked olefin rubber (B) whose Mooney viscosity (at 127 deg.C) is 5-300, iodine value is 30 or less and ethylene content is 35-85wt.% in the presence of an org. peroxide (C) whose half-life temp. is 160-220 deg.C at 170-220 deg.C for 30-120sec. Then, the component A, a halogenated butyl rubber (D) whose halogen content is 0.5-4.0wt.%, Mooney viscosity (at 100 deg.C) is 30-100 and degree of unsaturation is 0.5-4.0mole% and a metal oxide and/or a metal chloride (E) are added to this blend and the mixture is dynamically heat-treated at 170-220 deg.C for 30-120sec to obtain the title compsn. contg. 100pts.wt. the sum of 80-60wt.% component A and 0-40wt.% component B and 5-30pts.wt. component D.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing thermoplastic resin compositions having good impact resistance, and in particular to a thermoplastic resin composition in which two different crosslinked rubbers are homogeneously dispersed in a polypropylene phase. The present invention relates to a method for producing a plastic resin composition.

[Conventional technology]

Compositions consisting of polyolefins and partially crosslinked rubber components have excellent properties as thermoplastic elastomers, such as heat resistance, mechanical strength, flexibility, and elasticity, so they are used for large molded products such as automobile bumpers. It is becoming widely used.

As such a thermoplastic elastomer,
No. 34210 discloses a dynamically partially cured thermoplastic blend of 60 to 80 parts by weight of monoolefin copolymer rubber and 40 to 20 parts by weight of polyolefin plastic. This thermoplastic blend is obtained by mixing the above components with a curing agent and curing the mixture while dynamically kneading the mixture at a curing temperature.

In addition, for example, a partially crosslinked composition consisting of a polyolefin and two rubber components (Japanese Patent Publication No. 54-23702
(Japanese Patent Publication No. 56-15743), a partially crosslinked composition in which a polyolefin is blended into a composition obtained by treating a polyolefin and a rubber component in the presence of an organic peroxide (Japanese Patent Publication No. 56-15743), a method for producing such a composition (Japanese Patent Publication No. 15743), Publication No. 56-15740) etc. have been proposed.

However, the organic peroxide used as the crosslinking agent used in the production of the above partially crosslinked thermoplastic elastomer composition is highly reactive, which makes it difficult to control the degree of crosslinking to an appropriate degree. Since chain scission also progresses at the same time, there are problems in that the physical properties of the composition deteriorate, the low molecular weight products produced have an adverse effect on paintability, and partial gelation causes rough skin on the molded product.

Furthermore, there was also the problem that free radicals caused by organic peroxides remained in the molded product, impairing thermal stability.

As a solution to these problems, Japanese Patent Application Laid-open No. 62-
No. 50354 contains (A) 10 to 90 parts by weight of polypropylene, (B) 90 to 10 parts by weight of halogenated butyl rubber.
(However, (A) + (B) = 100 parts by weight), (C) 10 to 120 parts by weight of olefin rubber and (D) 5 to 120 parts by weight of mineral oil softener, (E)
An olefin-based soft resin composition is disclosed, which is obtained by heat-melting and kneading in the presence of a metal oxide and/or metal chloride, and then uniformly blending (F) polyolefin into the kneaded product.

[Problem that the invention seeks to solve]

However, although the composition of JP-A No. 62-50354 has good moldability, impact resistance, paintability, flexibility, mechanical strength, etc., it still lacks the performance required for automobile bumper materials, etc. It turned out to be insufficient.

Therefore, an object of the present invention is to provide a method for producing a thermoplastic resin composition in which the above-mentioned properties are further improved.

[Means for solving problems]

As a result of intensive research in view of the above problems, the present inventors first crosslinked a blend of polypropylene and crosslinked olefin rubber with organic peroxide, then mixed halogenated butyl rubber and polypropylene, and discovered that metal oxide and /or crosslinking halogenated butyl rubber in the presence of a metal chloride;
Alternatively, the inventors have discovered that a thermoplastic resin composition excellent in the above properties can be obtained by mixing after crosslinking, and have conceived the present invention.

That is, the first method for producing the thermoplastic resin composition of the present invention includes (a) dynamically heat-treating polypropylene and crosslinked olefin rubber in the presence of an organic peroxide to produce a kneaded product. Then, (b) polypropylene, halogenated butyl rubber, and metal oxide and/or metal chloride are added to the kneaded product, and the halogenated butyl rubber is crosslinked while being dynamically heat-treated.

Further, the second method for producing the thermoplastic resin composition of the present invention includes:
(a) dynamically heat-treating polypropylene and crosslinked olefin rubber in the presence of an organic peroxide to produce a first kneaded product; A second kneaded product containing crosslinked halogenated butyl rubber is added to the kneaded product and kneaded.

The materials used in the method for producing the thermoplastic resin composition of the present invention are as follows.

(A) Polypropylene Propylene homopolymer or ethylene, 1-butene,
It is a random or block copolymer mainly composed of propylene copolymerized with α-olefin such as 1-pentene, 1-hexene, and 4-methyl-1-pentene. Its melt flow rate (MFR) is 0.3 to 80
g/10 minutes, preferably 3 to 70 g/10 minutes, more preferably 15 to 70 g/10 minutes.

The polypropylene component contributes to improving the heat resistance and mechanical strength of the thermoplastic resin.

(B) Crosslinked olefin rubber ethylene, propylene, 1-butene, 1-hexene, 4
- Copolymer rubber consisting of two or more monoolefins such as methyl-1-pentene (
Typical examples include ethylene-propylene copolymer rubber), two of the above monoolefins (ethylene and propylene are preferred), dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, etc. Copolymer rubbers with non-conjugated diolefins or conjugated diolefins such as butadiene and isoprene are included. In addition, polyisoprene, nitrile rubber, etc. are also included. Olefin rubber is ML+-e (1
Those having a Mooney viscosity of 5 to 300 (27°C), an iodine number of 30 or less, and an ethylene content of 35 to 85% by weight are preferred.

The crosslinked olefin rubber component is present in the composition as a partially crosslinked rubber and improves its heat-resistant rigidity, mechanical strength, impact resistance, flexibility, etc.

(C) Halogenated butyl rubber means halogenated inbutylene-isoprene copolymer rubber. The mo1% of isobutylene and isoprene in the copolymer is generally 99.5:0.5 to 96:4.

Examples of halogen include chlorine or bromine atoms, and the halogen content is usually 0.5 to 4.0% by weight.

Mooney viscosity ML of matahalogenated butyl rubber, 8 (
100℃) is 30-100, and the degree of unsaturation is 0.5-100.
Preferably, it is 4.0 mol%.

The halogenated butyl rubber component is a rubber that can be crosslinked with metal oxides or metal chlorides, and is dispersed in the composition as a crosslinked rubber to form a network structure, and has excellent scratch resistance, heat resistance, oil resistance,
Provides rubber elasticity, gas impermeability, slip resistance, etc.

(D) The organic peroxide used for crosslinking the organic peroxide crosslinked olefin rubber has a half-life temperature of 160 to 220°C, such as ditert-butyl peroxide, dicumyl peroxide, and benzoyl peroxide. oxide, 2,5-
Examples include dimethyl-2,5-di(tert-butylperoxy)-hexane-3,2,5-dimethyl-2,5-di(tert-butylperoxy)-hexane.

In the treatment of partial crosslinking of olefin rubber using the organic peroxide, it is desirable to use a crosslinking aid such as p,p''-dibenzoylquinone dioxime or divinylbenzene.

The organic peroxide partially crosslinks the crosslinked olefin rubber to improve its rigidity at high temperatures. Further, the crosslinking aid acts to cause the crosslinking reaction to proceed uniformly and slowly.

(B) Metal oxide, metal chloride (crosslinking agent) Examples of the metal oxide include zinc oxide, magnesium oxide, lead oxide, calcium oxide, etc., and zinc oxide is preferred.

Examples of metal chlorides include zinc chloride and tin chloride. In addition, to prevent corrosion of molds etc. due to free halogen,
It is desirable to use magnesium oxide or the like as a halogen scavenger.

It is preferable to blend other marginal ingredients.

(F) Mineral oil softener High boiling point petroleum distillates used to reduce the hardness and increase flexibility and elasticity of vulcanized rubber, including paraffinic, naphthenic, and aromatic ones. .

In particular, paraffinic and naphthenic mineral oil softeners are preferred for use in materials to be coated because they do not adversely affect coating properties.

(G) In addition to the above ingredients, stabilizers such as antioxidants, ultraviolet absorbers, and metal deterioration inhibitors, lubricants, antistatic agents, electrical property improvers, flame retardants, and processing agents may be added as necessary. Additives such as sex improvers, pigments, talc, calcium carbonate, barium sulfate,
Inorganic fillers such as mica and calcium silicate can be blended.

Next, the manufacturing process of the thermoplastic resin composition of the present invention will be explained.

(1) First step Polypropylene and crosslinked olefin rubber are dynamically heat treated in the presence of an organic peroxide and, if necessary, a crosslinking aid, to crosslink the olefin rubber.

The dynamic heat treatment is preferably carried out by kneading at 170 to 220°C in an extruder or the like. The kneading time (residence time) is between 30 and 120 seconds, preferably between 60 and 120 seconds.

In order to carry out the next second step continuously, an extruder having two feed sections (hoppers) is used. This extruder is the first
As shown in the figure, first hopper 1, first kneading zone 2)
It has a second hopper 3 and a second kneading zone 4. The above materials introduced from the first hopper 1 are kneaded in the first kneading zone, but in order to prevent the organic peroxide from decomposing the halogenated butyl rubber introduced from the second hopper 3. Then, conditions are set so that most of the organic peroxide is consumed in the first kneading zone 2.

The polypropylene used in the first step is 3 to 15% by weight based on the final thermoplastic resin composition (hereinafter simply referred to as the final product), and the crosslinked olefin rubber is 5 to 30% by weight based on the final product. %. The organic peroxide is added in a proportion of 1 to 4 parts by weight per 100 parts by weight of the crosslinked olefin rubber. Preferred ranges include 3 to 10% by weight of polypropylene, 5 to 20% by weight of crosslinked olefin rubber, and 1.5 to 4 parts by weight of organic peroxide based on 100 parts by weight of crosslinked olefin rubber. It is.

(2) Second step Polypropylene, halogenated butyl rubber, and metal oxide and/or metal chloride are charged from the second popper 3 of the extruder shown in Fig. 1, and kneaded with the kneaded material coming from the first kneading zone 2. do. In this case, since most of the organic peroxide used in the first step has been consumed, crosslinking of the halogenated butyl rubber in the second step will be carried out using metal oxides and/or metal chlorides. The dynamic heat treatment conditions in the second step are - numerically a temperature of 170 to 220 °C and a residence time of 30 to 120 seconds, preferably 180 °C.
Temperatures of ˜200° C. and residence times of 30-60 seconds.

In the second step, a crosslinked olefin rubber may be added in addition to the above components, and a mineral oil softener may be added to improve the flexibility of the composition. In addition, rubbers that decompose with organic peroxides, such as polyisoprene rubber, may be added, and if necessary, halogen scavengers,
Antioxidants and the like are also added.

The blending amounts of each component in the second step are 10 to 70% by weight of polypropylene and 2 to 30% by weight of halogenated butyl rubber, preferably 30 to 50% by weight of polypropylene and 3 to 3% by weight of halogenated butyl rubber, based on the final product. ~
It is 150% by weight. When crosslinked olefin rubber is added, it is added in an amount of 5 to 30% by weight, preferably 5 to 15% by weight, based on the final product. Furthermore, the mineral oil softener is present in an amount of 2 to 15% by weight, preferably 2 to 8% by weight of the final product.

The total amount of metal oxides and/or metal chlorides is 20 to 40 parts by weight, preferably 20 to 25 parts by weight, per 100 parts by weight of halogenated butyl rubber.

In the second step, the polyolefin, halogenated butyl rubber, metal oxide and/or metal chloride, and their functional additives may be introduced from the second hopper 3 and kneaded directly into the kneaded material coming from the first kneading zone 2. Alternatively, the ingredients for the second step may be kneaded in advance and then charged from the second hopper 3. When kneading in advance, each component is blended with the above composition and kneaded in a separate extruder, Banbury mixer, or the like.

In addition, part of the polypropylene to be added and halogenated butyl rubber are dissolved and kneaded in the presence of metal oxides and/or metal chlorides to crosslink the halogenated butyl rubber, and this is mixed with the remainder of the polypropylene (if necessary, crosslinked olefin (along with rubber and other components) may be introduced from the second hopper 3 and kneaded with the first kneaded material coming from the first kneading zone 2.

〔Example〕

The present invention will be explained in further detail by the following examples.

In each Example and Comparative Example, physical property values were measured as follows.

(1) MFR: JIS K 7210 (Load 2
．． 16kg, 230°C) (2) Tensile strength and elongation at break: JIS K 6301 (3) Flexural modulus: JIS K 7203 (4)
Izotsu impact strength: JIS K 7110 (5)
Shore hardness: JIS K 7215 (D method) (6)
Moldability: ■Molding conditions Injection molding machine Mitsubishi Natco 350MV
500kg/Cm2 Injection time 13 seconds Molding cycle 38 seconds Gate Side gate molded product 3 mm x 10Qmm x 35
Qmm flat plate ■ Judgment criteria flow mark ○: Not generated △: Very slightly generated ×: Significantly generated (7) Paintability: Painting process After cleaning the test piece with trichloroethane vapor for 1 minute,
Primer [Re-291 manufactured by Nippon B Chemical Co., Ltd.]
was painted and baked at 100°C for 30 minutes. Next, urethane paint (R- manufactured by Nippon B Chemical Co., Ltd.) was applied on top of this.
257) and baked at 100°C for 30 minutes.

evaluation According to JIS K 5400 goban test.

The materials used in the following production examples, examples, and comparative examples are as follows.

Polypropylene M I = 70 g/10 min block voline Propylene (ethylene content 17% by weight) Ethylene containing Exxon V-5630C Ethylene pyrene resin content 65% by weight, oil containing ene copolymer amount 30 phr, Mooney viscosity ML (EP
DM) +. , (127°C") = 35) Ethylene-containing Exxon MD806C ethylene pyrene rubber with a content of 60% by weight and Mooney viscous (EP)
R) Degree ML1. a (127°C) = 30) Chlorinated butyl Chlorobutyl rubber manufactured by Exxon
-1066 (Mooney viscosity ML, .8 (CI I
R) (125°C) = 55) Organic peroxide
Perhexine-2,5B [2,5-dimethyl2,5-
Di(t-butylperoxy)hexyne] Crosslinking aid Dipinylbenzene styrene-E Shell Chemical Co., Ltd., Kraton G styrene-butylene 1657 Ren-styrene block copolymer (SEBS) Linear low-density carbon Nippon Unicar M GS -381 Liethylene [density = 0.92) M I = 20g/1
0 minutes] (LLDPE) Production Example 1 Production of crosslinked product 1 Ethylene-propylene-diene copolymer comb (E P
DM), 14 parts by weight of chlorinated butyl rubber, and 30 parts by weight of paraffin oil as a mineral oil softener were put into a Banbury mixer, and heated at 130 to 140°C for 3 hours.
The mixture was melt-kneaded for a minute. Next, 18 parts by weight of polypropylene was added, and kneading was continued at the same temperature.

Furthermore, as a crosslinking agent, Zn00.2 parts by weight, ZnCl
20°8 parts by weight, 0.5 parts by weight of Mg, and 1 part by weight of Ir-10100 as an antioxidant were added.
The crosslinking reaction was carried out at a temperature of 40° C. for 6 minutes.

The thus obtained crosslinked product 1 was taken out of the mixer and then pelletized by a conventional method.

Production Example 2 Production of Crosslinked Product 2 A crosslinked product 2 having the following composition was produced by the same method as Production Example 1.

Polypropylene 18 parts by weight EPDM
14” Chlorinated Butyl Rubber
38 Mineral oil softener 30 Zn0 6 ZnCl2 3 ”MgO1,5/
/ I r -10100,1〃 Example 1 9 parts by weight of polypropylene, 21 parts by weight of EPDM, 0.3 parts by weight of organic peroxide (verhexin-2,5B), 0.5 parts by weight of crosslinking aid (divinylbenzene) After sufficiently mixing the components in advance with a rotary mixer, the mixture was supplied to the first kneading zone 2 from the first hopper 1 of a twin-screw extruder having the structure shown in FIG. The kneading temperature in the first kneading zone 2 was maintained at 200° C. and the residence time was maintained at 60 seconds. Next, the second kneading zone 4
A mixture of 50 parts by weight of polypropylene and 120 parts by weight of a separately produced crosslinked product of halogenated butyl rubber was supplied to the reactor.

The residence time in the second kneading zone 4 was 30 seconds.

MFR, flexural modulus, tensile strength at break, tensile elongation at break, Izot impact strength,
Shore hardness, moldability and paintability were measured. The results are shown in Table 1.

Examples 2 to 5 Polypropylene/EPDM supplied to first kneading zone 2
The same method as in Example 1 was used, except that the heavy fluorescent ratio of , the polypropylene/crosslinked material 10 weight ratio added to the second kneading zone 4, and the resin amount ratio of the first kneading zone/second kneading zone were changed. A thermoplastic resin composition was manufactured and the same measurements as in Example 1 were performed. The results are shown in Table 1.

Examples 6 to 7 Among the resins supplied to the first kneading zone, EPDM was
The method of Example 1 and Example 2 was followed except that PR was used. Table 1 shows the measurement results for the obtained thermoplastic resin composition.

Examples 8 to 12 Thermoplastic resin compositions were obtained according to Example 1, using crosslinked product 2 with a high chlorobutyl content in place of chlorobutyl crosslinked product 1 supplied to the second kneading zone. Table 1 shows the measurement results for the obtained thermoplastic resin composition.

Examples 13 to 14 Thermoplastic resin compositions with a high rubber content were obtained by changing the resin formulations in each of the first kneading zone and the second kneading zone. Table 1 shows the measurement results for the obtained thermoplastic resin composition.

Example 15 Of the materials supplied to the second kneading zone, a portion of polypropylene and crosslinked product 2 was reduced, and a styrene-ethylene-butylene-styrene block copolymer (SEBS
) was added as in Example 1. Table 1 shows the measurement results for the obtained thermoplastic resin composition.

Example 16 The procedure of Example 15 was followed except that butyl rubber (IIR) was added to the second kneading zone. Table 2 shows the measurement results for the obtained thermoplastic resin composition.

Example 17 Linear low density polyethylene (LLDPE) was added to the second kneading zone.
) was added according to Example 15. Table 2 shows the measurement results for the obtained thermoplastic resin composition.

Table 2 Example 18 0.3 parts by weight of organic peroxide (perhexine-2,5B) in 9 parts by weight of polypropylene and 21 parts by weight of EPDM
Parts by weight and 0.5 parts by weight of a crosslinking aid (divinylbenzene) were added, thoroughly mixed with a rotary mixer, and then supplied to the first kneading zone. The reaction conditions were the same as in Example 1.

Next, in the second kneading zone, 54 parts by weight of polypropylene, 3 parts by weight of chlorinated butyl rubber, 8 parts by weight of EPDM, 5 parts by weight of a mineral oil softener, and 0.4 parts by weight of Zn○ as a crosslinking agent for chlorinated butyl rubber/Z A mixture of 2 parts by weight of nCl2O/0.1 parts by weight of Mg○ was fed to carry out crosslinking of the chlorinated butyl rubber in this zone. The same measurements as in Example 1 were performed on the obtained thermoplastic resin composition. The results are shown in Table 3.

Example 19 Similar to Example 18, chlorinated butyl rubber was crosslinked in the second kneading zone. The resin composition of the second kneading zone is polypropylene/chlorinated butyl rubber/EPDM=54/8
/ 3 (parts by weight), crosslinking agent ZnO/Z n C12
The same procedure as in Example 18 was performed except that /Mg O = 1.2/0.6/0.3 (parts by weight). The measurement results are shown in Table 3.

Table 3 Comparative Example 1 Polypropylene/EPDM/crosslinked product 1 was blended to have the same composition as the thermoplastic resin composition obtained in Example 1, and organic peroxide (Verhexin-2 ,5B)
0.3 parts by weight and 0.3 parts by weight of crosslinking aid (divinylbenzene).
After adding 5 parts by weight and uniformly dispersing the mixture, it was supplied to the first kneading zone of the extruder. The residence time in the extruder was 60 seconds.

Comparative Example 2 The blending ratio of the resin components was the same as in Comparative Example 1, and kneading was performed with the crosslinking agent and crosslinking aid reduced to 0.1 part by weight and 0.17 part by weight, respectively. Other conditions were the same as in Comparative Example 1.

Comparative Example 3 After blending the final composition so that the blending ratio was the same as in Example 2, and uniformly dispersing 0.3 parts by weight of the crosslinking agent and 0.5 parts by weight of the crosslinking aid, Comparative Example The mixture was kneaded according to 1.

Comparative Example 4 Kneading was performed in the same manner as in Comparative Example 1, except that Crosslinked Material 2 was added in place of Crosslinked Material 1 in Comparative Example 1.

Comparative Example 5 Based on the resin formulation of Comparative Example 4, kneading was performed with the crosslinking agent and crosslinking aid reduced to 0.1 part by weight and 0.17 part by weight, respectively.

Comparative Example 6 Material performance was investigated in the case where the resin mixture supplied to the second kneading zone did not contain a chlorinated butyl rubber crosslinked product.

Comparative Example 7 Crosslinking was performed using only an organic peroxide with a composition of polypropylene/E P DM = 55/45 (weight/liter ratio).

Comparative Example 8 Polypropylene and EPDM were charged into the first kneading zone at the blending ratio shown in Table 4 and kneaded at 200°C for 60 seconds (residence time). A thermoplastic resin composition was obtained in the same manner as in Example 1 by adding polypropylene and Crosslinked Material 1.

Comparative Example 9 In Comparative Example 8, 0.3% organic peroxide was added to the second kneading zone.
A thermoplastic resin composition was obtained in the same manner except that part by weight and 0.5 part by weight of the crosslinking aid were added.

Comparative Example 10 After kneading the components of the composition shown in Table 4 in the first kneading zone, polypropylene, EPDM, organic peroxide and crosslinking aid were further added in the blending ratio shown in Table 4 in the second kneading zone, A thermoplastic resin composition was obtained by kneading.

The basic physical properties, moldability, and paintability of the thermoplastic resins and compositions of Comparative Examples 1 to 10 above were measured. The results are also shown in Table 4.

〔Effect of the invention〕

As described above, in the method for producing a thermoplastic resin composition of the present invention, a mixture containing a crosslinked olefin rubber is first crosslinked with an organic peroxide, then a mixture containing a halogenated butyl rubber is added, and then metal oxidation is performed. In order to crosslink with compounds and/or metal chlorides or add them after crosslinking, the crosslinked olefin rubber is sufficiently crosslinked, and the halogenated butyl rubber is not decomposed by organic peroxides, and metal oxides and /or crosslinked with metal chlorides. In this way, a thermoplastic resin composition having excellent mechanical strength, heat resistance, impact resistance, flexibility, moldability, paintability, etc. can be obtained.

Because the thermoplastic resin composition obtained by the method of the present invention has the above-mentioned properties, it can be used as a substitute for polyurethane, polyester elastomer, etc., especially for large injection molding applications such as automobile bumpers, air ducts, door protectors, etc. Suitable for use in molded products.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of a twin screw extruder used to carry out the method of the present invention. 1...First hopper 2...First kneading zone 3...Second hopper 4...Second kneading zone Applicant Person Toa Fuel Industry Co., Ltd. company

Claims (5)

[Claims] (1) Contains 80 to 60% by weight of polypropylene, 20 to 40% by weight of crosslinked olefin rubber, and 5 to 30 parts by weight of halogenated butyl rubber based on 100 parts by weight of the polypropylene + the crosslinked olefin rubber. In a method for producing a thermoplastic resin composition, (a) polypropylene and a crosslinked olefin rubber are dynamically heat-treated in the presence of an organic peroxide to produce a kneaded product, and then (b) polypropylene and a halogen A method characterized in that halogenated butyl rubber and a metal oxide and/or metal chloride are added to the kneaded material, and the halogenated butyl rubber is crosslinked while being dynamically heat-treated. (2) The method according to claim 1, wherein the polypropylene in step (a) is 60% by weight or more based on the total amount of the thermoplastic resin composition. (3) Contains 80 to 60% by weight of polypropylene, 20 to 40% by weight of crosslinked olefin rubber, and 5 to 30 parts by weight of halogenated butyl rubber based on 100 parts by weight of the polypropylene plus the crosslinked olefin rubber. In a method for producing a thermoplastic resin composition, (a) polypropylene and crosslinked olefin rubber are dynamically heat-treated in the presence of an organic peroxide to produce a first kneaded product, and then (b) A method characterized in that a second kneaded product containing polypropylene and halogenated butyl rubber crosslinked with a metal oxide and/or a metal chloride is added to the first kneaded product and kneaded. (4) In the method according to claim 3, the second kneaded product in step (b) contains 2 to 3 times the crosslinked olefin rubber based on the total amount of the thermoplastic resin composition.
A method characterized by containing 0% by weight. (5) In the method according to claim 3 or 4, the polypropylene in step (a) is 1 to 15% by weight based on the total amount of the thermoplastic resin composition.
A method characterized in that